VIII INTERNATIONAL FORUM ON INDUSTRIAL SAFETYVIII INTERNATIONAL FORUM ON INDUSTRIAL SAFETYSaint Petersburg 24 Saint Petersburg 24 –– 27 May 201027 May 2010

““ SafeSafemmanagementanagementof an industrial process including of an industrial process including exothermic reactions and gaseous ammonia generationexothermic reactions and gaseous ammonia generation””

Giorgio Mari, Roberto Lauri Italian National institute for safety and health, Roma, Italy (www.ispesl.it)

Carmela MetapontePharmacy Faculty, University of Rome “La Sapienza”

Viro RomaniBiosint, Via del Murillo, 16, Sermoneta, Italy

УправлениеУправление безопасностьюбезопасностью производственногопроизводственного процессапроцесса, , включающеговключающего

экзотермическиеэкзотермические реакцииреакции ии выделениевыделение паровпаров аммиакааммиака

ДжорджиоДжорджио МариМари, , инженеринженер

ГосударственныйГосударственный институтинститут ИталииИталии попо вопросамвопросам безопасностибезопасности трудатруда ((ИталияИталия) )

� OVERVIEW OF THE PROBLEM

� GENERAL DESCRIPTION OF THE METHOD

� CHEMISTRY

� STUDY OF THE PROCESS BY REACTION CALORIMETER

� MASS AND ENERGY BALANCE

� SCALE-UP TO INDUSTRIAL SIZE

� REASONING OF: QUALITY – ECONOMY; SAFETY; ENVIRONMENT

� PROCESS SEQUENCE

� EXISTING REACTOR CHOICE AND PLANT ADJUSTMENT

� DESCRIPTION OF SOME TECHNICAL SOLUTIONS IN THE PLANT

�CONCLUSIONS

EUROPEAN COUNCIL DIRECTIVES 96/82/EC + EUROPEAN COUNCIL DIRECTIVES 96/82/EC + 2003/105/EC ON THE CONTROL OF MAJOR2003/105/EC ON THE CONTROL OF MAJOR--

ACCIDENT HAZARDS INVOLVING ACCIDENT HAZARDS INVOLVING DANGEROUS SUBSTANCES (SEVESO)DANGEROUS SUBSTANCES (SEVESO)

� AUTHORIZATION

� INSPECTIONS (PERIOD ABOUT 2 YEARS)

�SAFETY REPORT

�SAFETY MANAGEMENT SYSTEM

� INSPECTION COMMITTEE (3 people)

� Ministry for the Environment

� Fire Brigades

� Institute for Safety and Health

CONVERSION OF THE HYDROCHLORIDE REACTANT CONVERSION OF THE HYDROCHLORIDE REACTANT ““AA”” TO BASETO BASE

BENZODIAZEPINE DERIVATE USED AS AN ANXIOLYTICBENZODIAZEPINE DERIVATE USED AS AN ANXIOLYTIC

ALKYLATIONALKYLATION

CATALYST (LiNHCATALYST (LiNH22) EXCESS DESTRUCTION) EXCESS DESTRUCTION

PRODUCT PRODUCT ““CC”” IS CONVERTED TO AN HYDROCHLORIDE FORMIS CONVERTED TO AN HYDROCHLORIDE FORM

REACTION CALORIMETER USED FOR THE PROCESS STUDY REACTION CALORIMETER USED FOR THE PROCESS STUDY ((MettlerMettler Toledo RC1)Toledo RC1)

TRIALS PERFORMED USING 2 LITRESTRIALS PERFORMED USING 2 LITRESSIMULATION OF THE CONDENSERSIMULATION OF THE CONDENSERSIMULATION OF THE AMMONIA TREATMENTSIMULATION OF THE AMMONIA TREATMENTCONTINUOUS ADDITION OF REACTANTS IS CONTINUOUS ADDITION OF REACTANTS IS SIMULATED IN SMALL STEPSSIMULATED IN SMALL STEPSCATALYST (LiNHCATALYST (LiNH22) DESTRUCTION IS SIMULATED) DESTRUCTION IS SIMULATEDENERGY BALANCEENERGY BALANCE�� AGITATION IS CONSIDEREDAGITATION IS CONSIDERED�� ADDITION OF ADDITION OF ““COLDCOLD”” REACTANTS IS CONSIDERED REACTANTS IS CONSIDERED �� THERMAL DISPERSION OF THE CALORIMETER IS THERMAL DISPERSION OF THE CALORIMETER IS

CONSIDEREDCONSIDERED�� THERMAL LOSS DUE TO THE CONDENSATION IS NOT THERMAL LOSS DUE TO THE CONDENSATION IS NOT

AUTOMATICALLY CONSIDEREDAUTOMATICALLY CONSIDERED

CALORIMETRIC TRIALSCALORIMETRIC TRIALS

GRAPHIC OF THE CALORIMETRIC TRIALSGRAPHIC OF THE CALORIMETRIC TRIALS

Batch and jacket temperatures chart during reactants (“A” + “B”) addition

GRAPHIC OF THE CALORIMETRIC TRIALSGRAPHIC OF THE CALORIMETRIC TRIALSHeat generation chart during reactants (“A” + “B”) addition

Discovered Slightly Exothermic: 12 kJ/kg reagents

GRAPHIC OF THE CALORIMETRIC TRIALSGRAPHIC OF THE CALORIMETRIC TRIALSHeat generation chart during catalyst (LiNH2) excess destruction

Discovered Exothermic: 53 kJ/kg water

INDUSTRIAL BATCHINDUSTRIAL BATCH

MASS AND ENERGY BALANCES WERE CALCULATEDMASS AND ENERGY BALANCES WERE CALCULATED

REACTOR: 3500 LITRESREACTOR: 3500 LITRES

SEVERAL PROBLEMS OF PHASES (WATER SEVERAL PROBLEMS OF PHASES (WATER VSVS. SOLVENT) . SOLVENT)

CHANGES, SEPARATIONS, SUSPENTIONSCHANGES, SEPARATIONS, SUSPENTIONS

““AA””++””BB”” REACTANTS MIXTURE IS PREPARED IN ANHYDROUS REACTANTS MIXTURE IS PREPARED IN ANHYDROUS

SOLVENT (IN ABSENCE OF CATALYST NO REACTION HAPPENS)SOLVENT (IN ABSENCE OF CATALYST NO REACTION HAPPENS)

�� ““AA””++””BB”” ARE TRANSFERRED IN A TANKARE TRANSFERRED IN A TANK

CATALYST SOLUTION PREPARATION IN THE REACTOR CATALYST SOLUTION PREPARATION IN THE REACTOR

REACTION TEMPERATURE: 80REACTION TEMPERATURE: 80°°C (TRIALS AT 110 C (TRIALS AT 110 °°C)C)

““AA””++””BB”” ADDITION IN THE REACTOR IS SLOW AND GRADUALADDITION IN THE REACTOR IS SLOW AND GRADUAL

RESIDUAL CATALYST (LiNHRESIDUAL CATALYST (LiNH22 ) DESTRUCTION IS ACHIEVED BY A ) DESTRUCTION IS ACHIEVED BY A

SLOW WATER ADDITIONSLOW WATER ADDITION

-1200 lt“A”+”B” transferredin a tank

“A”+”B” unloaded

Atm+4-200 kg“B” load

-900 mmHg+45Evaporated solventis dropped in

reactor

Residual water< 0.1% Karl Fisher

water is completelyremoved

Solvent evaporation and condensation

Atm+4-300 ltLoading and furtherseparation ofdemi water

2° washing

Atm+4-300 ltLoading and furtherseparation ofdemi water

1° washing

-Aqueous phaseunloading

Phases separation throughdecantation

Atm+4-700 kg“A” disolvs in the solvent

Solvent load

-“A” in suspension“A” conversion to “base”

Atm+4-300 lt-Caustic soda 20% load

Atm+4-170 kg(powder)

-“A” Hydrochloride load

Atm+ 4-200 lt-Demineralized water load

AtmAmbAirGaseous Nitrogen-Nitrogen padding

pressureT°C

VentMaterial movedNotesProcess step

Atm+25-Aqueous phasecontaining the

product (250 kg)

Decantation + filtrationDecantation and separation ofthe aqueous phase

Atm+25-Demi water 160 ltHCl 15%

“C” becomesHydrochloride and

disolves in the aqueous phase

Conversion of “C”

5 mmHg abs+70Solvente + “A”condensationand removal

Solvent + “A”Precise Pressure trendReactant “A” excess distillationFINISH

60 mmHg abs+50Solvente + “A”condensationand removal

Solvent + “A”“A” excess removal(distillation)

Reactant “A” excess distillationSTART

Atm+30Water + salts300 lt

((decantationdecantation))2° Aqueous phase Elimination

Atm+30-Demi water300 lt

Further washing2° Salts “washing”

Atm+30Water + salts300 lt

((decantationdecantation))1° Aqueous phase Elimination

Atm+50-Demi water150 lt

Salts disolve in the aqueous phase

1° Salts “washing”

Atm+50NH3 to treatmentDemi water150 litres@ 50 lt/h

Generation of LiOHand NH3

Catalyst (Lithium amide) excessdestruction

Atm+80NH3 to treatment (solvent

condensation)

1200 lt@ 300 lt/h

Alkylation ReactionReactants continuous addition in the reactor

Atm+4-25 kgCatalystCatalyst LiNH 2 load

Atm+4-400 ltDry solvent load

pressureT°C

VentMaterial movedNotesProcess step

REACTOR HEAD COOLING EXCHANGERS

POWDER ADDITION POWDER ADDITION SYSTEMSYSTEM

� ROTATING MECHANISM

� NITROGEN INJECTION PIPES

� PNEUMATIC BARRIER REACTOR / ENVIRONMENT

� NITROGEN PADDING ALWAYS ACTIVE

GLASS LINED BAFFLE

� CROSS SECTION “C” SHAPED . (CEPП) – good for suspensions

� pH MEASURE

� MEMBRANE PUMP

� TEMPERATURE MEASURE

� NITROGEN BUBBLING

� SAFE SAMPLING

REACTANTS REACTANTS ““AA””++””BB”” ARE GRADUALLY ADDED IN THE REACTOR.ARE GRADUALLY ADDED IN THE REACTOR.A PUNCTUAL AND GRADUAL ADDITION OF THEM IS ENSURED BY A PROPER A PUNCTUAL AND GRADUAL ADDITION OF THEM IS ENSURED BY A PROPER

INSTRUMENTATION INSTRUMENTATION

PRESSURE CONTROL ON THE PUMP DISCHARGE BY FREQUENCY VARIATOR (INVERTER)

FLOWRATE IS CONTROLED BY A MASS-FLOW-METER AND A CONTROL VALVE (FACILITATED BY THE CONSTANT PRESSURE)

� GASEOUS AMMONIA HAS TO BE REMOVED AS MUCH AS POSSIBLE

� SOLVENT HAS TO BE CONDENSED AS MUCH AS POSSIBLE

� AMMONIA IS MORE SOLUBLE IN THE COLD SOLVENT !!!

!!��CONDENSATION IS DONE AT 2 DIFFERENT TEMPERATURES (+40CONDENSATION IS DONE AT 2 DIFFERENT TEMPERATURES (+40°°C C AND THEN +5AND THEN +5°°C) IN ORDER TO MAXIMIZE THE AMMONIA REMOVAL C) IN ORDER TO MAXIMIZE THE AMMONIA REMOVAL FROM THE BATCHFROM THE BATCH�� AT THE SAME TIME A GOOD CONDENSATION OF THE SOLVENT IS AT THE SAME TIME A GOOD CONDENSATION OF THE SOLVENT IS ACHIEVED ACHIEVED �� 2 CONDENSATORS IN SERIES OPERATE AT +40 AND +52 CONDENSATORS IN SERIES OPERATE AT +40 AND +5°°CC

PROCESS IS MANAGED IN PROCESS IS MANAGED IN ORDER TO ENSURE AN ORDER TO ENSURE AN OUTLET AMMONIA OUTLET AMMONIA FLOWRATE, WHICH ALLOWS FLOWRATE, WHICH ALLOWS A PROPER OPERATION OF A PROPER OPERATION OF THE ABSORPTION COLUMNSTHE ABSORPTION COLUMNS

�� REACTANTS “A”+”B” ARE GRADUALLY ADDED IN THE REACTOR

� CONTROLLED AND GRADUAL DESTRUCTION OF LITHIO AMIDE

� AMMONIA CONVERTION TO AMMONIUM SULPHATE

CONCLUSIONSCONCLUSIONS

� POTENTIALLY DANGEROUS PROCESS

� METHOD FOLLOWED

� DETAILED STUDY OF THE PROCESS BY CALORIMETRIC TRIALS.

� TRIALS ARE PERFORMED WITH A QUANTITY WHICH ALLOWS A REALISTIC SIMULATION OF THE INDUSTRIAL PROCESS

� MASS AND ENERGY BALANCE CALCULATION

� SCALE UP TO INDUSTRIAL PROCESS

� SAFE TECHNICAL SOLUTION IN THE INDUSTRIAL PLANT

спасибоспасибо заза вниманиевнимание

Giorgio Mari Giorgio Mari giorgio.mari@ispesl.itgiorgio.mari@ispesl.it

Roberto LauriRoberto Lauri

Carmela Carmela MetaponteMetaponte

Viro RomaniViro Romani